Solutions and methods for inhibiting corrosion

ABSTRACT

A corrosion inhibitor comprising a dispersant, an imidazoline, an amide, an alkyl pyridine and a heavy aromatic solvent. The resultant blend effectively inhibits corrosion of flow lines containing low pH mixtures of hydrocarbons, water, and acid gases.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to solutions and processes for inhibitingcorrosion. More specifically, this invention relates to solutions andprocesses for inhibiting corrosion of flow line surfaces that contain amixture of hydrocarbons, water, and acid gases.

2. Description

Petroleum refiners have long sought a solution to corrosion of flow linesurfaces that contain highly acidic mixtures of hydrocarbons, water, andacid gases such as carbon dioxide (CO₂), hydrogen chloride (HCl), andhydrogen sulfide (H₂ S). Refiners have had particular difficultypreventing corrosion caused by highly acidic mixtures, specificallythose mixtures having a pH lower than 4-5, in refinery distillationtower overhead streams. As the steam in the overhead gas from a tower iscondensed into liquid water at the surface of condensation equipment,some of the acid gases also condense and become dissolved in the liquidwater or water phase. The resulting aqueous solution is highly acidicand thus corrodes the tower overhead piping, vessels, pumps, exchangers,and other equipment that will be familiar to one skilled in the art.

The conventional solution to the problem of inhibiting corrosion hasbeen to add a neutralizing agent to the mixture of hydrocarbons, water,and acid gases to raise the pH. Such neutralizing agents have includedammonia and neutralizing amines, such as diethanolamine,methoxypropylamine, and morpholine. Some equipment operators have foundthat adding filming amines to the neutralizing amines further reducescorrosion of flow line surfaces.

Unfortunately, conventional filming amine corrosion inhibitors areineffective in the low pH environment of petroleum refinery toweroverhead streams. The conventional practice of adding neutralizingamines to elevate pH such that conventional filming amine corrosioninhibitors may be used has proved unsatisfactory. Above a pH of five(5), many naturally soluble species such as iron sulfide (FeS) and ironcarbonate (FeCO₃) form insoluble deposits that reduce the size of flowpaths and eventually plug the equipment by totally blocking the flowpath. Also, neutralizing amines may react to form corrosive salts anddeposits that plug the flow lines of tower overhead piping andequipment. Therefore, the application of neutralizing amines inconjunction with conventional filming amines that do not inhibitcorrosion in low pH environments has not satisfactorily solved theproblem of inhibiting corrosion. The addition of neutralizing aminesmust be done judiciously, using as little neutralizing amine as possibleto avoid possibly plugging equipment with deposits. In addition,reducing the amount of neutralizing amines used significantly reducesthe overall cost of using the equipment to make a product, asneutralizing amines are relatively expensive.

Refiners have also had problems with conventional corrosion inhibitorsthat form oil/water emulsions. Water is typically separated fromhydrocarbon streams, such as gasoline, to avoid contamination of thehydrocarbon product. Conventional corrosion inhibitors that formoil/water emulsions cause undesirable water entrainment in hydrocarbonstreams. Thus, there is a need for a corrosion inhibitor that has littletendency to form oil/water emulsions.

Yet another problem with conventional corrosion inhibitors is inadequatedistribution of the corrosion inhibitor throughout the corrosive stream.Conventional water-soluble corrosion inhibitors fail to adequatelydistribute themselves in a flow line that contains predominantlyhydrocarbons in a hydrocarbon/water mixture. Poor distribution ofconventional corrosion inhibitors causes inadequate corrosion protectionof the piping and equipment surfaces because the chemical simply doesnot get to where it is needed. Thus, a need has long existed for acorrosion inhibitor that distributes itself evenly throughout apredominantly hydrocarbon stream and yet effectively prevents corrosionin the acidic aqueous phase. Solubility of the corrosion inhibitor inthe hydrocarbon stream to which the inhibitor is added is a desirablecharacteristic. Because hydrocarbon solubility of a corrosion inhibitorenhances adequate distribution within the equipment to be protected,there is a need for a corrosion inhibitor that is hydrocarbon solubleyet still protects against corrosion in an aqueous phase.

Thus, there is a need for a corrosion inhibitor that (1) inhibitscorrosion at low pH ranges, (2) is soluble in hydrocarbons such that thecorrosion inhibitor is adequately distributed through the corrosivestream, (3) provides protection against corrosion in the aqueous phaseof the fluid contained in the piping and equipment to be protected, and(4) does not cause an oil/water emulsion problem in the fluid containedin the flow lines to be protected, and more particularly, in the piping,condensers, pumps, vessels and other equipment in a distillation toweroverhead system.

SUMMARY OF THE INVENTION

The present invention satisfies the need for a corrosion inhibitor that(1) inhibits corrosion at low pH ranges, (2) is soluble in hydrocarbonsuch that the inhibitor adequately distributes through the corrosionstream, (3) provides protection against corrosion in the aqueous phaseof the fluid contained in the flow lines to be protected, and (4) doesnot cause an oil/water emulsion problem in the fluid contained in theflow lines to be protected, and more particularly, in the piping,condensers, pumps, vessels, and other equipment in a distillation toweroverhead system.

The present invention is a corrosion inhibitor composition whichincludes the following chemicals in a mixture: a pentane-solubleimidazoline, a pentane-soluble amide, a pyridine-based compound, apentane-soluble dispersant, and a solvent.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features, aspects and advantages of the presentinvention will become better understood with regard to the followingdescription, appended claims and accompanying drawings where:

FIG. 1 is a schematic of an injection system in which the presentinvention is used;

FIG. 2 is a schematic of the system used to test the solutions andmethods of the present invention for the inhibition of corrosion;

FIG. 3 is a cutaway view of the electrochemical corrosion cell used inthe system shown in FIG. 2; and

FIG. 4 is a graph showing the corrosion inhibiting result of the presentinvention.

Additional objects, advantages and novel features of the invention willbe set forth in part in the description which follows, and will becomeapparent to those skilled in the art upon examination of the followingor may be learned by practice of the invention.

DETAILED DESCRIPTION

The solutions and methods of inhibiting corrosion of the presentinvention may be implemented by the use of a typical corrosion inhibitorinjection system shown in FIG. 1. Such injection systems are commonlyused with conventional corrosion inhibitors, such as neutralizing aminesand filming amines. Operators using conventional corrosion inhibitorswith this typical system may be able to use the solutions and methods ofthe current invention with few hardware changes to their plant.

In the typical corrosion inhibitor injection system shown schematicallyin FIG. 1, the corrosion inhibitor is injected up flow from the surfacesof the flow lines to be protected. As used hereinafter, the term "flowline" shall include piping 150, 154, 156, condensers 58, reflux drums66, reflux pumps 64, and other piping, vessels, pumps, condensers, andequipment that contain a corrosive agent, such as an acid gas dissolvedin an aqueous mixture.

The corrosion inhibitor is typically stored in a pot 50 from which ametering pump 52 is used to inject the corrosion inhibitor into the flowlines (as defined above) to be protected. To best protect distillationtower overhead piping and equipment, the corrosion irhibitor is addedinto the tower overhead vapor line 54 between the top of the tower 56and the inlet 57 to the overhead gas condensers 58. The corrosioninhibitor is typically diluted with a slipstream 60 of hydrocarbon fromthe reflux drum 66.

The present invention is directed to solutions for inhibiting corrosioncomprising solutions, blends or mixtures of: a pentane-solubleimidazoline, a pentane-soluble amide, a pyridine-based compound selectedfrom the group consisting of pyridine, monoalkyl pyridines, dialkylpyridines, and trialkyl pyridines where the alkyl groups have one tothree carbon atoms; a pentane-soluble dispersant, particularly adispersant formula marketed under the trademark DMAD by BuckmanLaboratories International, Inc., 1256 N. McLean Blvd., Memphis, Tenn.has been used; however, equivalent dispersants generally designated aspentane-soluble, amide-based dispersants may be used; and a solvent,particularly a solvent that is designated as Advasol 150 marketed byAdvanced Aromatics, Inc. of 5501 Baker Road, Baytown, Tex.; 77521 hasbeen used; however, equivalent solvents generally designated as heavyaromatic solvents having a boiling point of 400-580 degrees Fahrenheitmay be used. As used herein, the term "boiling point" refers to theboiling point at 760 millimeters of mercury absolute pressure. It willbe understood by one skilled in the art that mixtures of theaforementioned pyridine-based compounds may be used. Also, thepentane-soluble amide may be an amide, diamide, triamide, or polyamide.The pentane-soluble imidazoline may include polyimidazolines. It will beunderstood by one skilled in the art that the aforementioned monoalkylpyridines, dialkyl pyridines, and trialkyl pyridines include thecompounds (and all isomers thereof) represented by the followingdiagrams: ##STR1## where X₁, X₂, and X₃ can be alkyl groups having oneto three carbons. In addition, the present invention is also directed toprocesses of inhibiting corrosion by the use of such blends.

While conventional filming amine corrosion inhibitors are ineffective inlow pH environments and must be used in conjunction with neutralizingamines, the present invention makes a major departure in the oppositedirection. Specifically, the present invention, although based on afilming amine, reduces or eliminates the amount of neutralizing aminerequired to achieve adequate corrosion protection. In an alternateembodiment, the present invention is enhanced by the addition of asmall, corrosion-inhibiting amount of a neutralizing amine.

It has been found that corrosion of flow lines containing hydrocarbons,water, and acid gases is inhibited by the present invention even whenthe pH of the corrosive mixture is below 4-5. Although otherconventional filming amine corrosion inhibitors are generallyineffective below a pH of 5, the corrosion inhibitor of the presentinvention is effective even at a pH below 4. Because the corrosioninhibitor of the present invention is effective at lower pH ranges, theamount of expensive neutralizing amine that must be added to the fluidcontained in the flow lines protected is substantially reduced. Thepresent invention eliminates or reduces the need for neutralizingamines, thus decreasing the risk of depositing solids in the piping andequipment in the distillation tower overhead system.

Another advantage of the corrosion inhibitor of the current invention isthat the corrosion inhibitor is soluble in light hydrocarbons that haveat least 5 carbons atoms (such as pentane). Notwithstanding the oilsolubility of the corrosion inhibitor of the present invention, thecorrosion inhibitor sufficiently disperses into the aqueous phase of thefluid in the flow lines to be protected. It is important that acorrosion inhibitor sufficiently disperse into the aqueous phase inorder to provide adequate corrosion protection.

Yet another advantage of the corrosion inhibitor of the presentinvention is its low tendency to form oil/water emulsions. The corrosioninhibitor of the present invention has a WSIM number greater than 80.The WSIM number is a standardized ASTM test parameter and is anindication of the tendency of a substance to entrain water in itshydrocarbon phase. The WSIM (water separation index modification) numberincreases as emulsion-forming tendencies decrease.

Specifically, the corrosion inhibitor of the present invention iscomprised of the following aforementioned components in the followingrespective compositions:

    ______________________________________    Component        Weight Percentage Ranges    ______________________________________    Pentane-soluble Imidazoline                     0.5-30    Pentane-soluble Amide                     0.5-30    Pentane-soluble Dispersant                     0.5-10    Pyridine-based compound                     1.0-50    Heavy Aromatic Solvent                      30-90    ______________________________________

The preferred composition is as follows:

    ______________________________________    Component         Weight Percentage    ______________________________________    Pentane-soluble Imidazoline                      5    Pentane-soluble Amide                      15    Pentane-soluble Dispersant                      5    Pyridine-based compound                      10    Heavy Aromatic Solvent                      65    ______________________________________

Because the components are mixed together as liquids, heating theliquids to lower their viscosity accelerates the mixing process. Thecomponents of the corrosion inhibitor of the present invention are mixedtogether until a homogenous mixture is obtained. No particular order ofmixing the components is required. A glass vessel is the preferredmixing container. The corrosion inhibitor of the present method is knownto be effective at temperatures up to 300 degrees Fahrenheit.

To use the described corrosion inhibitor mixture, the corrosioninhibitor of the present invention is continuously added to the fluidcontained in the flow lines to be protected in an amount sufficient toprevent corrosion. It has been found that a corrosion inhibiting dose of5-25 parts per million by volume (ppmv) of the corrosion inhibitor isgenerally sufficient to provide an effective level of corrosionprotection. In the preferred mode, the corrosion inhibitor iscontinuously added to the fluid contained in the flow line to beprotected to maintain a corrosion inhibiting amount of 6-9 ppmv of thecorrosion inhibitor. When the present invention is used in its preferredmode with a distillation tower overhead system such as that shown inFIG. 1, the corrosion inhibitor of the present invention is diluted witha slipstream 60 of hydrocarbon in a ratio of 10 parts by volumehydrocarbon to 1 part by volume corrosion inhibitor. When used in atower overhead system, the preferred hydrocarbon slipstream 60 is towerreflux 62 from the discharge of the reflux pump 64.

Although continuous addition of the corrosion inhibitor is generallypreferred, batchwise addition of a corrosion-inhibiting amount of thecorrosion inhibitor of the present invention may also be used.

The corrosion inhibitor of the present invention has been used inapplications with a variety of fluid velocities through the flow line tobe protected. The present invention has been found to be effective atfluid velocities up to 25 feet per second.

EXAMPLES Example 1 Preparation of Corrosion Inhibitor of PresentInvention

In the preferred embodiment, the components of Table 1 were first heatedindividually until fluid and then blended until homogenous in a glasscontainer. Preparation of corrosion inhibitors using other relativeamounts of imidazoline, amide, pyridine-based compounds, pentane-solubledispersant, and heavy aromatic solvent is similar to the proceduredescribed above.

                  TABLE 1    ______________________________________                    Weight Percentage    ______________________________________    Pentane-soluble Imidazoline                      5    Pentane-soluble Amide                      15    Pyridine-based compound                      10    Pentane-soluble Dispersant                      5    Heavy Aromatic Solvent                      65    ______________________________________

In the preferred embodiment listed in Table 1, the imidazoline was abis-imidazoline with the formula: ##STR2## where R₁ and R₂ were selectedfrom the group consisting of all hydrocarbons having twelve to eighteencarbon atoms;

the amide had the formula: ##STR3## where R₃ was selected from the groupconsisting of all hydrocarbons having twelve to eighteen carbon atoms;

the pyridine-based compound was selected from the group consisting ofpyridine, monoalkyl pyridines, dialkyl pyridines, and trialkyl pyridineswhere the alkyl groups have one to three carbon atoms; thepentane-soluble dispersant was a dispersant marketed under the trademarkDMAD by Buckman Laboratories International, Inc., 1256 N. McLean Blvd.,Memphis, Tenn.; and the solvent was a heavy aromatic solvent designatedas Advasol 150 marketed by Advanced Aromatics, Inc. of 5501 Baker Road,Baytown, Tex. 77521.

Example 2 Corrosion Test

The corrosion inhibiting characteristics of the present invention wereevaluated in the flow loop system 80 shown in FIG. 2. Corrosion rates ofsteel test coupons 200 (FIG. 3) contained in corrosion test cell 88 weremeasured before and after injection of the corrosion inhibitor of thepresent invention. As indicated by the results shown in the graph ofFIG. 4, the corrosion inhibitor of the present invention inhibitedcorrosion of the test coupons 200 even in a low pH environment.

As illustrated in FIG. 2, an acid gas comprising approximately 98.5 mole% methane, 1.0 mole % carbon dioxide and 0.5 mole % hydrogen sulfide wasstored in a cylinder 82. An aqueous mixture with a pH of 2 was preparedby mixing liquid water with a sufficient amount of hydrochloric acid inthe water container 84. The acid gas was sparged through the aqueousmixture in the water container 84 for at least three hours. The acid gaswas also sparged through a test oil of heptane in an oil container 86for at least three hours.

Valve B 87, valve C 90, valve D 92, and valve E 94 were closed and valveA 96 was opened. Acid gas from the cylinder 82 was also used to pressurethe aqueous mixture from the water container 84 and the test oil fromthe oil container 86 into the flow loop 120. The resulting oil/watermixture in the flow loop was 80 percent by volume aqueous mixture and 20percent by volume test oil, both such components being at leastpartially saturated with acid gas.

The pump 98 was turned on to circulate the oil/water mixture containedin the flow loop 120. The oil/water mixture was discharged from the pump98 and caused to flow through valve A 96. From valve A 96, the oil/watermixture passed through the mass flow meter 102 and into the autoclave100. The autoclave 100 heated the oil/water mixture to 80° C.

When the flow loop mixture reached the desired temperature, valve A 96was closed and valve B 87 and valve C 90 were opened to establish flowfrom the discharge of the pump 98 through valve C 90. After exitingvalve C 90, the oil/water mixture entered the electrochemical cell 88.The electrochemical cell 88, also shown in FIG. 3, used a standardelectrochemical technique, specifically, linear polarization resistance,to measure the corrosion rate of test coupons 200.

After passing through the electrochemical corrosion cell 88, theoil/water mixture passed serially through valve B 87 and the mass flowmeter 102 to the autoclave 100. After exiting the autoclave 100, theoil/water mixture flowed back to the suction of the pump 98. With theoil/water mixture circulating through the flow loop 120 in this manner,a baseline corrosion rate of the coupons 200 in the corrosion cell 88was thus established for between 15 and 20 hours.

After establishment of the baseline corrosion rate, the corrosioninhibitor under evaluation was added to the oil/water mixture. A 50parts per million by volume dosage of corrosion inhibitor was added tothe oil/water mixture by pouring the inhibitor into a flexible hose 104,connecting the hose across valve D 92 and valve E 94, and opening valvesD 92 and E 94. With the pump 98 circulating the oil/water mixturethrough the flexible hose 104, the corrosion inhibitor was blended withthe oil/water mixture. The corrosion rates were monitored after theaddition of the corrosion inhibitor.

As demonstrated by the results shown on FIG. 4, the corrosion inhibitorcomposition of Example 1 dramatically reduced the corrosion rate.Specifically, introduction of the corrosion inhibitor at about 18 hoursreduced the corrosion rate from approximately 400 mils per year toapproximately 20 mils per year where it remained for an additional timeperiod of approximately 20 hours.

Example 3 Emulsion Data

American Society for Testing and Materials method D 3948-87, which willbe familiar to those skilled in the art, was used to evaluate theemulsion tendency of the corrosion inhibitor of the present invention.The blends described in Table 2 were prepared in a fashion similar tothat described in Example 1.

The results of testing of the present invention are shown on Table 2.The MSEP (micro separometer rating) number reported was converted to aWSIM number. WSIM is a commonly-used test parameter for determining thetendency of a substance to form an emulsion with water.

                  TABLE 2    ______________________________________    Emulsification Data    Blend Component       Run #1  Run #2    ______________________________________    Heavy Aromatic Solvent, Vol. %                          53      65    Pentane-soluble Amide, Vol. %                          27      15    Pentane-soluble Imidazoline, Vol. %                          5       5    Pyridine-based compound, Vol. %                          10      10    Pentane-soluble Dispersant, Vol. %                          5       5    Dosage of Corrosion Inhibitor of                          10      10    Present Invention, parts per million by    volume.    MSEP                  80      80    WSIM Number           >80     >80    ______________________________________

The corrosion inhibitor of the present invention is effective forinhibiting corrosion of petroleum refinery distillation tower overheadpiping and equipment. Specifically, the corrosion of the presentinvention is most effective for preventing corrosion of flow lines thatcontain a mixture of hydrocarbon streams containing acid gases such ascarbon dioxide, hydrogen sulfide, and hydrogen chloride in the presenceof water. In the preferred mode, the corrosion inhibitor of the presentinvention is used in corrosion inhibiting dosages to prevent corrosionof flow lines made of mild steel, admiralty brass, or stainless steel.It will be understood by one familiar in the art that the presentinvention may be used to protect surfaces of other metallurgies.

The objects and advantages of the invention may be realized and attainedby means of the instrumentalities and combinations particularly pointedout in the accompanying drawings and appended claims.

I claim:
 1. A corrosion inhibitor composition comprising:a. apentane-soluble imidazoline; b. a pentane-soluble amide selected fromthe group consisting of pentane soluble amides, diamides, triamides, andpolyamides; c. a pyridine-based compound selected from the groupconsisting of pyridine, monoalkyl pyridines, dialkyl pyridines, andtrialkyl pyridines where the alkyl groups have one to three carbonatoms; d. an amide-based, pentane-soluble dispersant; and e. a heavyaromatic solvent having a boiling point of 400-580 degrees Fahrenheit,said imidazoline amide, pyridine-based compound, dispersant, and solventbeing present in said composition in selective amounts sufficient toimpart to said composition a WSIM value greater than
 80. 2. Thecorrosion inhibitor composition of claim 1, wherein the imidazolinecomprises a bis-imidazoline having the formula: ##STR4## where R₁ and R₂are selected from the group consisting of all hydrocarbons having twelveto eighteen carbon atoms.
 3. The corrosion inhibitor composition ofclaim 1, wherein the amide has the formula: ##STR5## where R₃ isselected from the group consisting of all hydrocarbons having twelve toeighteen carbon atoms.
 4. The composition of claim 1, wherein thecomposition contains 0.5 to 30 weight percent of a bis-imidazolinehaving the formula: ##STR6## where R₁ and R₂ are selected from the groupconsisting of all hydrocarbons having twelve to eighteen carbon atoms.5. The composition of claim 1, wherein the composition contains 0.5 to30 weight percent of an amide having the formula: ##STR7## where R₃ isselected from the group consisting of all hydrocarbons having twelve toeighteen carbon atoms.
 6. The composition of claim 1, wherein thecomposition contains 0.50 to 10 weight percent of an amide-based,pentane-soluble dispersant.
 7. The composition of claim 1, wherein thecomposition contains one to fifty weight percent of a pyridine-basedcompound selected from the group consisting of pyridine, monoalkylpyridines, dialkyl pyridines, and trialkyl pyridines where the alkylgroups have one to three carbon atoms.
 8. The composition of claim 1,wherein the composition contains thirty to ninety weight percent heavyaromatic solvent having a boiling point of 400-580 degrees Fahrenheit.9. A corrosion inhibitor composition comprising:a. about five weightpercent bis-imidazoline having the formula: ##STR8## where R₁ and R₂ areselected from the group consisting of all hydrocarbons having twelve toeighteen carbon atoms; b. about fifteen weight percent amide having theformula ##STR9## where R₃ is selected from the group consisting of allhydrocarbons having twelve to eighteen carbon atoms; c. about fiveweight percent amide-based, pentane-soluble dispersant; d. about tenweight percent pyridine-based compound selected from the groupconsisting of: pyridine, monoalkyl pyridines, dialkyl pyridines, andtrialkyl pyridines where the alkyl groups have one to three carbonatoms; and e. about sixty-five weight percent heavy aromatic solventhaving a boiling point of 400-580 degrees Fahrenheit,wherein saidcorrosion inhibitor composition has a WSIM value greater than
 80. 10.The corrosion inhibitor composition of claim 1, further comprising acorrosion inhibiting amount of a neutralizing amine.
 11. A process formaking a corrosion inhibitor comprising mixing together in proportionssufficient to achieve a WSIM value greater than 80 at least one eachof:a. a pentane-soluble imidazoline; b. a pentane-soluble amide selectedfrom the group consisting of pentane soluble amides, diamides,triamides, and polyamides; c. a pyridine-based compound selected fromthe group consisting of pyridine, monoalkyl pyridines, dialkylpyridines, and trialkyl pyridines where the alkyl groups have one tothree carbon atoms; d. an amide-based, pentane-soluble dispersant; ande. a heavy aromatic solvent having a boiling point of 400-580 degreesFahrenheit.
 12. The process of claim 11, wherein the imidazoline is abis-imidazoline having the formula: ##STR10## where R₁ and R₂ areselected from the group consisting of all hydrocarbons having twelve toeighteen carbon atoms.
 13. The process of claim 11, wherein the amidehas the formula: ##STR11## where R₃ is selected from the groupconsisting of all hydrocarbons having twelve to eighteen carbon atoms.14. A product made by the process of claim 11, wherein the productcontains: 0.5 to 30 weight percent of a bis-imidazoline having theformula: ##STR12## where R₁ and R₂ are selected from the groupconsisting of all hydrocarbons having twelve to eighteen carbon atoms.15. A product made by the process of claim 11, wherein the productcontains 0.5 to 30 percent of an amide having the formula: ##STR13##where R₃ is selected from the group consisting of all hydrocarbonshaving twelve to eighteen carbon atoms.
 16. A product made by theprocess of claim 11, wherein the product contains 0.50 to 10 weightpercent of an amide-based, pentane-soluble dispersant.
 17. A productmade by the process of claim 11, wherein the product contains one tofifty weight percent of a pyridine-based compound selected from thegroup consisting of: pyridine, monoalkyl pyridines, dialkyl pyridines,and trialkyl pyridines where the alkyl groups have one to three carbonatoms.
 18. A product made by the process of claim 11, wherein theproduct contains thirty to ninety weight percent of a heavy aromaticsolvent having a boiling point of 400-580 degrees Fahrenheit.
 19. Acorrosion inhibitor composition suitable for protection of refinerydistillation tower overhead systems operating at pH levels lower than 4comprising:a. five weight percent bis-imidazoline having the formula:##STR14## where R₁ and R₂ are selected from the group consisting of allhydrocarbons having twelve to eighteen carbon atoms; b. fifteen weightpercent amide having the formula ##STR15## where R₃ is selected from thegroup consisting of all hydrocarbons having twelve to eighteen carbonatoms; c. five weight percent amide-based, pentane-soluble dispersant;d. ten weight percent pyridine-based compound selected from the groupconsisting of: pyridine, monoalkyl pyridines, dialkyl pyridines, andtrialkyl pyridines where the alkyl groups have one to three carbonatoms; and e. sixty-five weight percent heavy aromatic solvent having aboiling point of 400-580 degrees Fahrenheit,wherein said corrosioninhibitor composition has a WSIM value greater than 80.